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Electrochemical Activation: a key to
ecologically pure technologies of water
treatment
Control of microbes in water treatment and
medicine: two sides of the same problem
Electrochemical Activation of Water and
Aqueous Solutions: Past , Present and
Future
STEL: history and new prospects
Disinfection of drinking water: problems
and solutions
WAYS TO IMPROVE THE EFFICIENCY AND
QUALITY OF PROCESSES OF PREPARING
OIL FOR REFINING USING
ELECTROCHEMICALLY ACTIVATED WATER
ELSOR Process to Extract Hydrogen Sul de
from Natural Gas
Application of ECA solutions and enzyme
preparations for hop extraction
Effect of electrochemically activated
systems on malt enzymes
APPLICATION OF ANK ANOLYTE IN CASES
OF INTESTINAL INFECTION
ELECTROCHEMICALLY ACTIVATED
SOLUTIONS IN VETERINARY PRACTICE
Issues of chemical composition and
operating properties of chlorine based
inorganic liquid chemical germicides
PREVENTION AND THERAPY OF
NOSOCOMIAL INFECTIONS USING
ELECTROCHEMICALLY ACTIVATED
SOLUTIONS
DISINFECTING MILITARY HOSPITAL
SURGERY UNIT WITH NEUTRAL ANOLYTE
DISINFECTION OF AIR-CONDITIONERS
WITH ANOLYTE SOLUTION
APPLICATION OF ELECTROCHEMICALLY
ACTIVATED SOLUTIONS IN THE TRAUMA
AND ORTHOPEDIC CLINIC
ECONOMIC PREREQUISITES FOR APPLYING
IN HEALTH INSTITUTIONS STEL
ELECTROCHEMICAL DEVICES FOR
SYNTHESIS OF WASHING, DISINFECTANT
AND STERILIZING SOLUTIONS
WAYS OF CREATING EFFECTIVE AND SAFE
ANTIMICROBIAL LIQUID AGENTS AND
EVOLUTION OF PUBLIC PERCEPTION OF
DISINFECTION MEASURES
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Electrochemical Activation: a New Trend in Applied Electrochemistry
V itold Bak hir Ele c troc he mic al
Syste ms an d Te c hn ologie s
Biography Electrochemical activation Inventions Publications History Contacts
Electrochemical Activation: a New Trend in Applied
Electrochemistry
Published in “Zhizn & Bezopasnost” Magazine (Life and Safety, rus.), N 3,
2002, p. 302 – 307.
A .P. Tomilov
Background. In 1802, 30 years before M. Faraday discovered the electrolysis
laws, Russian academician V. V. Petrov discovered, through using a high-
voltage galvanic battery he had developed, that emission of electrolysis gases
near the electrodes is accompanied by acidification of water near the anode
and alkalization of water near the cathode. V. V. Petrov divided the space
between the anode and the cathode with a porous diaphragm, and for the first
time ever obtained water rich with products of mostly cathodic or chiefly
anodic electrochemical reactions: catholyte and anolyte, respectively.
In 1807-1808, G. Davy, an English researcher, obtained novel, previously
unknown metals sodium and potassium through electrolysis. Later electrolysis
was used to obtain magnesium and aluminum.
In 1837, a member of the Russian Academy of Sciences, academician B. S.
Jacobi published his report on the galvanoplasty method he had developed:
production of metal copies of relief items via electrolysis. This discovery
became the basis for commercial copper refining.
First electrochemical copper refineries were built in the 1870s after the
dynamo had been invented. In 1886 – 1888, factories emerged to
electrolytically produce aluminum and hypochlorous acid salts. In 1890, plants
were put into operation, to electrolytically produce chlorine, alkali, and metal
sodium, and then for hydrogen and oxygen production via water electrolysis,
for production of electrolytic nickel, copper and zinc.
Currently, electrolysis of aqueous salt solutions, melts, manufacture of
chargeable elements and galvanic batteries is one of the largest industries: the
electrochemical industry. The scope of the electrochemical industry is versatile.
The most important deliverables are:
refining of nonferrous and noble metals;
production of nonferrous metals from ores;
production of alkali, alkali-earth and other light metals;
generation of hydrogen, oxygen, chlorine and alkalis;
electrolytic synthesis of inorganic and organic substances;
ornamental and corrosion-resistant coatings/plating for metals;
manufacture of electric accumulators, galvanic batteries and other
chemical electricity sources;
dimensional electrochemical machining of metals and alloys.
Virtually all chlorine (the global production is about 50 mln tpa), almost all
caustic soda, metals such as magnesium and aluminum are produced using
electrochemical processes which also play an important role in the metallurgy
of copper, zinc, cadmium, nickel, tin, sodium, beryllium, zirconium, indium,
and in production of some noble metals, including gold.
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E cacy and Safety of Liquid Chemical
Germicides Applied for All-levels
Disinfection (Sterilization), Pre-sterilizing
Treatment.
Evolution of technical systems for
electrochemical activation of liquids
Electrochemical Activation: a New Trend in
Applied Electrochemistry
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Electrochemical Activation: a New Trend in Applied Electrochemistry
The majority of the most important modern electrochemical sites comprise
large-scale electrolyzers or electroplating bathes spread over extensive areas
of thousands of square meters, interconnected into a single production
complex with a network of piping and electric lines. The operation of this
complex is maintained by a broad range of auxiliary facilities: water treatment,
preparation of initial solutions, conditioning of electrolysis products, waste
regeneration and neutralization etc.
What impeded the discovery of electrochemical activation? Virtually all
electrolytic solutions used in applied electrochemical processes have high
concentrations and low specific electrical resistance, which is stipulated by the
requirements to minimize the electricity consumption per unit of the product
generated.
Since fresh water or low-mineralized initial solutions did not find any practical
use as electrolytic solutions in applied electrochemistry, an opinion have been
formed in more than a century of its development, that fresh water cannot be
electrolyzed due to its low content of ions. This notion was based on the
traditionally established approaches to commercial electrochemical processes,
where the range of used voltages did not usually exceed 6 Volts at a current
strength of several hundreds of Amperes on the electrodes of a single element.
In fact, fresh, ultra-fresh and even distilled water can be electrolyzed, but it
requires high voltage between the electrodes, while the water electrolytic
decomposition goes on at a low current density i.e. at a very high wasteful (in
term of industrial electrolysis) electricity consumption.
How the phenomenon of electrochemical activation was discovered? In
1972, engineer V. M. Bakhir first mentioned a previously unknown fact: the
anolyte and catholyte generated from low-mineralized water in a diaphragm
electrochemical reactor, have physical and chemical parameters and reactivity
which differ quite strongly from those of model catholyte and anolyte prepared
through dissolution of chemicals in water (with the type and the quantity of
the chemicals being determined according to the classical electrolysis laws).
Further research showed that the differences between the properties of freshly
prepared catholyte and anolyte of diluted aqueous salt solutions and their
chemical model counterparts (solutions of stable alkalis or acids) are not
constant and stable over time. Upon some time (the relaxation time) the
qualities and the reactivity of anolyte and catholyte through spontaneous
changes become identical to the corresponding parameters of their chemical
models, i.e. in the end the electrolysis laws are strictly met, even though not
immediately but after quite a long period: generally from tens of minutes to
tens or even hundreds of hours.
These discovered significant differences in reactivity and physical and chemical
parameters allowed V. M. Bakhir to name the anolyte and catholyte during
their relaxation period as "activated", or, in other words, electrochemically
activated solutions (water) and to formulate the basic principles of the
electrochemical activation technology.
Electrochemical activation: the phenomenon and the technology.
Electrochemical activation as a physical & chemical process is a complex of
electrochemical and electrophysical impacts acting on water and the ions and
molecules of the dissolved substances, under conditions of the minimum heat
emission, in the area of volume charge near the electrode (either anode or
cathode) surface of an electrochemical system, when the charge transfer by
electrons across the 'electrode-electrolyte' border is non-equilibrium.
The electrochemical activation causes water to transform into a metastable
(activated) state characterized by unusual values of chemical and physical
parameters including the oxidation-reduction potential (connected with the
activity of electrons in water, electric conductivity, pH and other parameters
and properties). The characteristics and qualities of water that have been
disturbed by a previous external exposure change spontaneously over time
and gradually reach equilibrium values through relaxation.
The process of generation of electrochemically-activated water and solutions is
classified as extremely non-equilibrium and is the subject of research of a new
intensively developing area in chemistry: the synergetics in chemical processes
and chemical technology. While the major goal of the applied electrochemistry
is to find parameters of the optimum approach to equilibrium for an
electrochemical process, for electrochemical activation it is important to
determine parameters of the optimum removal from the electrochemical
reaction equilibrium conditions.
Electrochemical activation as a technology is the production and further
utilization of electrochemically activated water either in the process of its water
treatment and purification, or as a medium or a reagent in versatile processes
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with a view to controlling
complicated physical &
chemical reactions; saving of
energy, time, and materials;
final product quality
improvement; and less waste
generation.

It is to be explained that the

term "water", from the
viewpoint of the
electrochemical activation
processes, means a diluted
aqueous solution of electrolytes
of simple or complex
composition, with a total
concentration from several
milligrams to several grams per
liter. Generally, this is both
distilled, and ultra-fresh, and
fresh, including drinking, and low-mineralized (process or service) water, i.e.
aqueous electrolytic solutions with the specific electric conductivity changing
greatly with a comparatively small change of concentration. Fig.1 shows a
generalized dependence of the specific electric conductivity on the
concentration for most of inorganic electrolytes: acids, alkalis, and salts.
Electrochemical activation effects are most prominent for aqueous solutions
with the electrolyte concentration below 0.1 mol/l; these effects are much
weaker in solutions with the electrolyte concentration above 0.1 mol/l.

It is to be noted, that the reaction products obtained from activated solutions,

generally do not change their properties and conditions with time, i.e. they are
not prone to relaxation processes. For example, if water with a high iron-ion
content reacts with an activated catholyte, and thrice more iron ions turn into
insoluble compounds than in the case of the same water reacting with a
chemical model of the catholyte, the reaction results are irreversible in both
cases.

Technical systems for electrochemical activation. Generally, when direct

electric current flows through water, chemical reactions always take place on
the electrodes, and the chemical composition of water near the anode and
cathode changes. The objective of electrochemical activation is to subject the
entire volume of liquid to the action of an electric field with the maximum
possible intensity at the maximum possible chemical exposure and the
minimum heat emission. This task is quite difficult, because the maximum
intensity of the electrophysical effect can only be ensured in the intimate
vicinity of the electrode surface, i.e. in the electric double layer (EDL) area, for
any electrochemical systems consisting of two electrodes immersed in liquid.

Hence, special electrochemical reactors are necessary to perform

electrochemical activation processes because conventional electrolyzers (both
laboratory and industrial) are designed to optimize the performance of
conventional applied electrochemical processes, and are not suitable for
operation with fresh water or diluted aqueous solutions. In fact, water only
gets activated in the immediate proximity to the electrode surface where the
electric field intensity in the electric double layer (EDL) reaches hundreds of
thousands Volts per cm.

EDL is very thin: it is about 0.1 m m in weak solutions and fresh water, and
much thinner in concentrated solutions. To understand clearer how difficult it is
to ensure the contact between all the micro-volumes of the water surrounding
the electrode and the electrode surface, let us assume that an electrode (a
metal rod with roughly a pen's diameter) is immersed into a beaker. If we also
assume that the high-intensity electric field area around the electrode (EDL)
would suddenly have expanded to 1 mm, the beaker diameter should have
increased from 7 cm to 700 m, to retain the proportions of the system. Of
course, all the water in this 'lake' cannot be processed near the electrode
surface, if special means are not applied.

First special technical devices for carrying out electrochemical activation (ECA),
diaphragm electrochemical reactors, were developed in 1974 – 1975 by V. M.
Bakhir and his colleague Yu. G. Zadorozhnii. Strenuous work to create an
optimum reactor design for electrochemical treatment of fresh water and
diluted aqueous solutions had been going on for almost 20 years, and resulted
in the creation of a basically new design, the flow-through electrochemical
modular FEM-1 cell, in the end of the 1980s – beginning of the 1990s.
However, the broad commercial application of the processes using
electrochemically activated solutions and water only became possible in the
recent 7-8 years due to the advent of a new type of industrial electrochemical
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systems based on flow-through electrochemical modular cells of the 3rd

generation (FEM-3, see Fig. 2) and RFE reactors (units of FEM-3 cells of
various configurations), which were also created by the above-mentioned
inventors.

The FEM cell differs from the known electrochemical

reactors in the following respects:

The FEM cell is modular, has small outline dimensions,

low weight, high productivity and economic efficiency;
the combination of these features allows a FEM-cell to
be used both in industrial and household technical
electrochemical systems.
The FEM cell diaphragm is made of zirconium- and
aluminum-based ceramics. It features a very high
strength, a low filtration capacity, which prevents
cathode and anode water volumes from physical
mixing, can withstand the trans-membrane pressure
gradient up to 1 at, with the electrode chamber sizes
kept unchanged.
The FEM cell diaphragm can adsorb positively-charged
particles on the surface facing the anode, and
negatively charged particles on the surface facing the
cathode. This causes a reduction in its electrical
resistance in diluted aqueous solutions and fresh
water, and hence decreases the power consumption as
well as makes durable work possible when there is
pressure gradients of opposite charges between the
electrode chambers. Due to this the diaphragm may
be used as an ion-selective partition in an
electrochemical reactor.

The FEM cell electrode chambers are annular

elongated spaces between the cylindrical surfaces of
the electrodes and the diaphragm. The ratio of their
dimensions ensures an equal average movement
velocity for liquid microvolumes in each cross-section,
and facilitates contact of the maximum possible
quantity of water microvolumes and the electrode
surface, i.e. the EDL area.
The optimal length to width ratio in the electrode
chambers in the FEM cell ensures that saturation of
solutions with gas in electrode chambers will have no
detrimental effect on the energetic and functional
characteristics of the FEM cell at a high current density
and a low liquid flowrate.
FEM cells in electrochemical water treatment devices Fig. 2. Section of the
can be hydraulically connected into a single hydraulic FEM cell: 1 - cathode;
chain without flow interruption not only in parallel, but 2- anode; 3 -
diaphragm
in series, too. This is not possible when using
conventional electrochemical reactors. Both anode and cathode chambers
of various FEM cells can be connected into the circuit arbitrarily and in any
order, and auxiliary devices (flotation, catalytic reactors; flow, pressure,
velocity, temperature control systems, etc.) can be cut in between the
elements as required.
FEM cells can be electrically connected in parallel, in series, or in series-
parallel. This allows the circuit to be easily switched when required from
bipolar electrolyzer to monopolar or bipolar-monopolar electrolyzer,
without changing the hydraulic configuration.

Conditions are created in the FEM cells for the major part of water
microvolumes to get treated within split seconds in a high-intensity field in the
EDL. This enables to obtain water with pronounced electron-acceptor
properties near the anode (oxidant water), whereas water with electron-donor
properties is generated near the cathode (antioxidant water). Both anolyte and
catholyte are kinds of water with an increased electric activity, which becomes
apparent in the following physical & chemical or biochemical reactions not only
as an independent factor, but as the catalyst increasing the activity of the
small amount of the products of anodic and cathodic reactions synthesized
during the electrochemical treatment process.

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Where is the electrochemical activation currently used? Since the
beginning of the 1990s, OAO “NPO EKRAN” and VNIIIMT (the Russian Scientific
and Research Institute for Medical Engineering) of the RF Ministry of Health
have been the leaders in the area of researches into electrochemical activation
and development of various processes based on electrochemically activated
media. A number of major scientific centers in Russia is also involved in this
problem, in co-operation with the above-indicated organizations. Currently, the
ECA phenomenon and technologies are studied throughout the world: in the
USA, the UK, Germany and some other countries.

STEL devices have become well recognized both in Russia and abroad: they
provide environment-friendly germicide and disinfectant solutions (ANK-type
anolyte) for medical and childcare outfits, public utilities, food industry,
swimming pools.

Table 1 compares the characteristics of the electrochemically activated ANK

anolyte produced in STEL devices and conventional disinfectant and germicide
chemicals.

Table 1

ANK anolyte and various disinfectant solutions: comparison of

characteristics

The results of the research completed in the Memorial Battelle Institute (USA)
provided convincing evidence of the advantages of electrochemically activated
ANK anolyte over conventional disinfectant solutions. Anthrax spores were
established to perish in the ANK anolyte within several seconds, while the
same result was obtained only after 30 min in a sodium hypochlorite solution
with the concentration of the active substance 12 times higher than in the ANK
anolyte.

Various modifications of EMERALD-type devices are well known: they provide

disinfected water with an improved composition to individual users, childcare
outfits, food industry and public catering facilities: this water is just as useful
as spring and best mineral waters. Table 2 shows the technical characteristics
of different designs/types of household medical EMERALD devices
commercially manufactured by OAO "NPO EKRAN". The dimensions of these
devices are 230´ 50´ 300 mm, the weight is about 1.9 kg, the power
consumption is 30 to 60 W.

Table 2.

Water treatment in EMERALD devices: quality indicators.

Maximum
permissible Relative pollutant
concentration concentrations in Purification
Pollutant description
(MPC) source water degree, %
according to (related to MPC)
WHO

Total microbe number, 50 – 100 2 - 10 > 99.9

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CFU/ml

Coli index, CFU/l 3 ~ 105 > 99.99

up to 100
Poliomyelitis virus, units/ml - > 99.99
units/ml

Trichloroethylene, mg/l 0.005 Up to 20 70-80

Tetrachloroethylene, mg/l 0.005 10 89

Benzene, mg/l 0.01 200 74

Surfactants, mg/l 0.5 7-8 94

Pesticides (DDT), mg/l - up to 10 mg/l 90

2 63

Aluminum, mg/l 0.5 8 75

> 10 97

1.5 70

Chromium, mg/l 0.05 10 95

> 100 > 99

3 70 – 80

Iron, mg/l 0.3 5 85

10 95

3–4 84
Copper, mg/l 1.0
20 - 30 80 to >99

5 97
Zinc, mg/l 5.0
10 > 99

Arsenic, mg/l 0.05 3 – 3.5 90

2.5 65

Lead, mg/l 0.03 3.5 78

> 10 > 95

6 85

Phenol, mg/l 0.001 10 - 20 50 – 70

> 100 80 - 96

2 19 – 43
Nitrates, mg/l 10
3 -3.5 up to 10

Nitrites, mg/l 1.0 1.0 80 - 99

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Trihalomethanes, mg/l 0.1 0.8 100

2 95

Additional resources of technical electrochemical activation systems.

Applying the flow-through electrochemical modular FEM cells to solve problems
of conventional applied electrochemical technologies, we were able to create a
basically new technology for on-site chlorine production. This technology was
implemented in AQUACHLOR devices, which have no analogs in the world. The
philosophy of the process realized in the AQUACHLOR devices is to feed 10¸
20% NaCl solution slowly, commensurable to the electrochemical reaction rate,
into the FEM cell anode chambers under the pressure of 0.5¸ 0.7 kgf/cm2.
Evolved gaseous chlorine is removed through a pressure regulator and sent to
users, for example, it is fed to an ejector mixer and gets dissolved to give
chlorine water. This chlorine water can further be used to disinfect natural
fresh water in water treatment facilities or to treat wastewater, while the
catholyte generated during pressure gradient-caused filtration of water and
sodium ions from the anodic chamber into the cathodic one through the porous
oxide-zirconium diaphragm is used as a detergent/cleaning agent or as a pH-
controlling agent in coagulation water treatment processes. It is to be
emphasized that energy and NaCl consumption in the AQUACHLOR device is
quite close to the theoretical limits. This makes this technology attractive not
only for local chlorine users, but for Cl commercial manufacturers, too.

References:

1. Bakhir V. M., Atadzhanov A. R., Mamadzhanov U. D., Alyokhin S. A.,

Mariampolsky N. A., Nadzhmitdinov A. Kh. Activated Substances. Some
Theoretical and Practical Issues // Bulletin of the Uzbek Academy of
Sciences. Series of technical sciences, 1981, No. 5. - p. 68-72.
2. Kirpichnikov P. A., Bakhir V. M., Gamer P. U., Dobren'kov G. A.,
Liakumovich A. G., Fridman B. S., Agadzhanian S. E. About the Nature of
Electrochemical Activation of Media // Reports of the USSR Academy
of Sciences, 1986. v. 286. No. 3. - p. 663-666.
3. Bakhir V. M., Zadorozhnii Yu. G. Electrochemical RFE Reactors. -M.:
Giperox, 1991. - 35 pp; - figures.
4. Bakhir V. M., Tsikoridze N. G., Spector L. Е. et al. Electrochemical
Activation of Aqueous Solutions and its Application in Food
Industry Processes. // Series: Food industry. -Tbilisi: Georgian Research
Institute for Scientific and Technical Information, 1988, issue 3. - 81 pp; -
figures
5. Bakhir V. M. Electrochemical Activation. - M.: VNIIIMT, 1992. – 2 parts
- 657 pp; - figures
6. Prilutsky V. I., Bakhir V. M. Electrochemically Activated Water:
Abnormal Properties, Biological Action Mechanism. - M.; VNIIIMT ,
1997. - 228 pp; - figures
7. Bakhir V. M. Medical Technical Systems and Technologies for
Synthesis of Electrochemically Activated Solutions. - M., VNIIIMT ,
1998. - 66 pp; - figures
8. Panicheva S. A. New Technologies for Sterilization and Disinfection
of Complicated Items Designed for Medical Use. - M., VNIIIMT , 1998.
- 122 pp; - figures
9. Bakhir V. M., Zadorozhnii Yu. G., Leonov B. I., Panicheva S. A., Prilutsky V.
I., Sukhova O. I. Electrochemical Activation: History, Status,
Prospects. -M.: VNIIIMT , 1999, - 256 pp.; - figures
10. Bakhir V. M. Modern Technical Electrochemical Systems for Water
Decontamination, Purification and Activation. – M.: VNIIIMT , 1999. –
84 pp; - figures
11. Leonov B. I., Prilutsky V. I., Bakhir V. M. Physical & Chemical Aspects of
Biological Action of Electrochemically Activated Water. -M.: VNIIIMT
, 1999. – 244 pp.; - figures
12. Bakhir V. M., Zadorozhnii Yu. G., Leonov B. I., Panicheva S. A., Prilutsky V.
I. Electrochemical Activation: Water Treatment and Production of
Useful Solutions. - M.: VNIIIMT , 2001. - 176 pp.; - figures

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